JPH10265471A - Pyridylpyrazole compound, its production and agricultural and horticultural fungicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of being industrially advantageously synthesized, processable into an agricultural and horticultural fungicide, having sure effects and safely usable. SOLUTION: This compound is shown by formula I (X is H, a halogen, cyano, a 1-6C alkyl, etc.; R is H, a metal atom, a 1-6C alkylcarbonyl, etc.; Z is a halogen, cyano, a 1-6C alkyl, etc.; (m) is 1-4) such as 3-cyano5-(3-chloro-2-pyridyl) pyrazole, etc. The compound is obtained by reacting a compound of formula II (X<1> is H or a 1-6C alkyl; R<1> is a 1-6C alkyl) with hydroxylamine to give a compound of formula III and reacting the compound with a dehydrating agent such as acetic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel pyridylpyrazole compound, a method for producing the same, and a fungicide for agricultural and horticultural use.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, a large number of control agents are used against crop diseases, but their use is insufficient due to insufficient control effect or the emergence of drug-resistant pathogens. Due to their limitations, their potential to cause phytotoxicity and contamination of plants, and their high toxicity to humans, fish and livestock, there are not many satisfactory control agents that are not always satisfactory. Therefore, there is a strong demand for a drug that can be safely used with few such disadvantages. As a technique related to the present invention, many pyrazole compounds have already been synthesized, but a compound having a 2-pyridyl group and a cyano group simultaneously as a substituent on the pyrazole ring has not been synthesized yet, and its bactericidal activity has not been reported. Not even known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyridylpyrazole compound which can be advantageously synthesized industrially and which can be used as a fungicide for agricultural and horticultural use which is surely effective and can be used safely.

[0004]

That is, the present invention provides:

[0005]

Embedded image

Wherein X is a hydrogen atom, a halogen atom, a cyano group, a C _1-6 alkyl group, a C _1-6 haloalkyl group,
Represents a _1-6 alkylthio group, a C _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group. R is a substituent on the nitrogen atom of the pyrazole ring, and is a hydrogen atom, metal atom, C _1-6 alkylcarbonyl group, C _1-6 alkylcarbonyloxymethyl group, C _1-6 alkylsulfonyl group, (halogen Atom, C _1-6 alkyl group or C
Benzoyl group (optionally substituted with _1-6 alkoxy group), (halogen atom, C _1-6 alkyl group or C _1-6
A benzoyloxymethyl group (optionally substituted with an alkoxy group) or a phenylsulfonyl group (optionally substituted with a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group). Z is a halogen atom, cyano group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6
Alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, di C _1-6 alkylamino group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _3-8 cycloalkyl group, C _3-8 cycloalkylmethyl group or C
Represents a _1-6 alkoxy group. m represents 1, 2, 3, and 4. A pyridylpyrazole compound or a salt thereof, a production method thereof, and an agricultural and horticultural fungicide containing the compound.

As the halogen atom for X, chlorine,
Bromine, fluorine and the like. _{Examples of the} C _1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl, and examples of the C _1-6 haloalkyl group include fluoromethyl, 1-fluoroethyl. 2
-Fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl, pentafluoroethylethyl and the like,
Examples of the C _1-6 alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, and butylthio, and examples of the C _1-6 alkylsulfinyl group include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, and butylsulfinyl.
t-butylsulfinyl and the like, as C _1-6 alkylsulfonyl groups, methylsulfonyl, ethylsulfonyl,
Propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl and the like.

[0008] As the metal atom in R, copper, zinc,
Examples include iron, tin, cobalt, nickel, and manganese. As the C _1-6 alkylcarbonyl group, acetyl,
And propionyl and the like, and C _1-6 alkylcarbonyloxymethyl groups include acetyloxymethyl, propionyloxymethyl, propylcarbonyloxymethyl, isopropylcarbonyloxymethyl, butylcarbonyloxymethyl, t-butylcarbonyloxymethyl and the like;
_{Examples of the} C _1-6 alkylsulfonyl group include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl and the like. Further, as a substituent of a benzoyl group, a benzoyloxymethyl group and a phenylsulfonyl group, a halogen atom is chlorine, bromine, fluorine or the like, and a C _1-6 alkyl group is methyl, ethyl, propyl, isopropyl or butyl. , Isobutyl, t-butyl and the like, and examples of the C _1-6 alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy and the like. In addition, the substituent may have two or more, and in this case, those substituents may be the same or different.

As the halogen atom for Z, chlorine,
Bromine, fluorine and the like; C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl; and C _1-6 haloalkyl groups such as fluoromethyl and 1-fluoroethyl. 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl,
Pentafluoroethylethyl and the like; C _2-6 alkenyl groups such as vinyl, 1-propenyl, allyl, crotyl and butadienyl; and C _2-6 haloalkenyl groups such as 1-chlorovinyl, 2-chlorovinyl and the like. 2-fluorovinyl, 3-chloroallyl, 2-Kurorokurochiru, and examples of the C _2-6 alkynyl group, ethynyl, 1-propynyl, 2-propynyl. Examples of C _2-6 haloalkynyl group, 2-chloro-ethynyl , 2-bromoethynyl,
3-chloro-2-propynyl, 3,3,3-trifluoro-1-propynyl. Examples of the di-C _1-6 alkylamino group, dimethylamino, diethylamino, ethyl isopropylamino and the like, C _1-6 alkylthio As a basis,
Methylthio, ethylthio, propylthio, isopropylthio, butylthio, t-butylthio and the like, and examples of the C _1-6 alkylsulfinyl group include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl and t-butylsulfinyl, and the like. _{Examples of the 1-6} alkylsulfonyl group include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-
Butylsulfonyl and the like. _{Examples of} the C _3-8 cycloalkyl group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and examples of the C _3-8 cycloalkylmethyl group include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, and cyclohexyl. Methyl and the like, and C _1-6 alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy and the like. When m is 2 or more, Z may be the same or different.

[0010] The salt of the pyridylpyrazole compound of the present invention refers to an agriculturally / horticulturally acceptable salt, and is not particularly limited as long as it is an agriculturally / horticulturally acceptable salt. For example, salts of alkaline earth metals such as magnesium and calcium, iron,
Metal salts such as copper, zinc, nickel, cobalt, tin, and manganese; and salts of acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, and methanesulfonic acid.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. Production method (i)

[0012]

Embedded image

(Where Z and m represent the same meaning as described above,
X ¹ represents a hydrogen atom or a C _1-6 alkyl group, R ¹
Represents a C _1-6 alkyl group. )

In this method, the compound represented by the general formula (4) and hydrazine are reacted without solvent or in an appropriate organic solvent.
By reacting at 50 to 150 ° C., general formula (2)
Is produced by reacting the compound with a hydroxylamine salt such as hydroxylamine hydrochloride or hydroxylamine sulfate or hydroxylamine in the presence of an acid in a solvent-free or suitable organic solvent. Derivation to the oximes represented by the formula (3), and further reaction with a carboxylic anhydride such as acetic anhydride and a dehydrating agent such as phosphorus pentoxide to give an oxime represented by the general formula (1 ′) This is for producing a cyanopyrazole compound. Examples of the solvent used here include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, diethyl ether, and tetrahydrofuran (THF).
Such as ethers, halogenated hydrocarbons such as chloroform, acetonitrile, dimethyl sulfoxide (DMS
O), N, N-dimethylformamide (DMF) and the like.

[0015]

Embedded image

[0016] (wherein, X ² represents a halogen atom, R ²
Represents a C _1-6 alkyl group, and Z and m represent the same meaning as described above. )

Among the compounds represented by the general formula (1 '),
The compound in which X is a hydrogen atom can be derived into a compound represented by the general formula (5) by halogenation by a general synthetic chemistry technique. In the compound represented by the general formula (5), after protecting the NH proton with a protecting group such as a 1-ethoxyethyl group as required, a trifluoromethyl group, a C _{1- 6} alkylthio groups can be introduced. Further, a C _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group can be converted by oxidizing a C _1-6 alkylthio group. Production method (ii)

[0018]

Embedded image

(Wherein, Z, X ² and m have the same meanings as described above, and X ³ represents a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a cyano group or a C _1-6 alkylthio group. Represents a group.)

In this method, a compound represented by the general formula (6) is halogenated by an ordinary synthetic chemistry method to thereby add a halogen atom to the 4-position of the pyrazole ring represented by the general formula (7). And then reacting with an organolithium such as BuLi and a formylating agent such as DMF, N-methyl-N-phenylformamide or formate to formyl represented by the general formula (8). Produce derivatives. Furthermore, by reaction with hydroxylamine at -50 to 150 ° C. in a solvent-free or suitable organic solvent, via a oxime represented by the general formula (9), a carboxylic acid anhydride such as acetic anhydride, pentoxide, etc. By reacting with a dehydrating agent such as phosphorus, general formula (1 ″)
To produce a 4-cyanopyrazole compound represented by the formula: Hydroxyamine can be used in the form of a salt such as a hydrochloride, a sulfate or the like, or in a free form using a salt of hydroxyamine with a base. Solvents that can be used in this reaction include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, ethers such as diethyl ether and THF, halogenated hydrocarbons such as chloroform, acetonitrile, DMSO, DMF. And the like.

[0021]

Embedded image

(Wherein X ⁴ is a C _1-6 alkyl group,
Represents a _1-6 haloalkyl group, R ³ represents a C _1-6 alkyl group, and Z and m represent the same meaning as described above. )

In the production method (ii), among the compounds represented by the general formula (6), those compounds in which X ³ is other than a cyano group are, as shown above, pyridine derivatives and hydrazine, respectively. Can be produced in the absence of a solvent or in a suitable organic solvent at -50 to 150 ° C. Examples of the solvent that can be used for the reaction include water, alcohols such as methanol and ethanol, and carboxylic acids such as acetic acid. The amount of hydrazine used is
0.5 to 3 equivalents are preferable for 1 equivalent of the pyridine derivative. Production method (iii)

[0024]

Embedded image

(Wherein, X, Z, and m have the same meanings as described above, R ⁴ represents a substituent obtained by excluding a hydrogen atom and a metal atom from R, and V represents a halogen atom.)

This method comprises reacting a compound represented by the general formula (10) with a compound represented by the general formula (11) in the presence of a base at -50 to 150 ° C. In 1), R is a compound other than a hydrogen atom and a metal atom. At this time, the general formula (1a)
And (1b) are obtained. Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide, metal alkoxides such as sodium methylate and potassium t-butoxide, and organic bases such as triethylamine and pyridine. And the like. Solvents that can be used here include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, diethyl ether,
Examples include ethers such as THF, halogenated hydrocarbons such as chloroform, acetonitrile, DMSO, DMF, and the like. The amount of the compound represented by the general formula (11) is 0.1% with respect to 1 equivalent of the compound represented by the general formula (10).
Preferably, 5 to 3 equivalents and 0.5 to 3 equivalents of the base are used.

Production method (iv) Among the compounds represented by the general formula (1), compounds in which R is a metal atom can be prepared by a general synthetic chemical method, for example, a compound represented by the general formula (10) It can be produced by dissolving in an organic solvent such as acetone or ethanol, and adding an aqueous solution of a metal salt such as a metal chloride or an ethanol solution thereto.

In the present invention, after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

[0029]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Preparation of 3-cyano-5- (3-chloro-2-pyridyl) pyrazole (Compound No. I-4)

[0031]

Embedded image

(A) 3-diethoxymethyl-5- (3-
Preparation of chloro-2-pyridyl) pyrazole 5.00 g (32.1 m) of 3-chloro-2-acetylpyridine
mol) and 6.80 g (38.6 mm) of ethyl diethoxyacetate
ol) in 30 ml of a THF solution, 9.92 g (51.4 ml) of a methanol solution of 28% sodium methoxide was added under ice cooling, and the mixture was stirred for 2.5 hours. Next, 1.36 g (7.72 mmol) of ethyl diethoxyacetate and 1.98 g (10.10 g) of a methanol solution of 28% sodium methoxide.
3 mmol) was added under ice-cooling, and the mixture was further stirred at room temperature for 17 hours. 3.70 g of acetic acid was added to the reaction solution, and the mixture was concentrated under reduced pressure. Water and ethyl acetate were added to the residue, and the mixture was separated. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude 1,3-diketone derivative 1
0.57 g was obtained. 7.71 g of this crude product was dissolved in 100 ml of ethanol, and hydrated with 1.29 g of hydrazine hydrate under ice cooling.
g (25.8 mmol) was added and the mixture was stirred under ice cooling for 4.5 hours. After evaporating the solvent and the like from the reaction solution under reduced pressure, water was added to the residue, and the mixture was extracted with chloroform and then with ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 3-diethoxymethyl-5- (3 4.57 g of (-chloro-2-pyridyl) pyrazole were obtained. 3-chloro-2-
69% overall yield from acetylpyridine n _D ^22.5 1.5598

(B) 3-hydroxyiminomethyl-5
Preparation of (3-chloro-2-pyridyl) pyrazole 1.50 g (5.32 mmol) of 3-diethoxymethyl-5- (3-chloro-2-pyridyl) pyrazole was dissolved in 20 ml of ethanol, and hydroxylamine hydrochloride was added. .74
g (10.6 mmol) was added and the mixture was refluxed for 4 hours. Sodium bicarbonate was added to the reaction solution, extracted with chloroform and ethyl acetate, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was washed with n-hexane and crystallized as 3-hydroxyiminomethyl-
0.77 g of 5- (3-chloro-2-pyridyl) pyrazole (mixture of isomers) was obtained. Yield 65%, melting point 215-216 ° C

(C) 3-cyano-5- (3-chloro-2)
Preparation of -pyridyl) pyrazole 3-hydroxyiminomethyl-5- (3-chloro-2-
To 0.57 g (2.56 mmol) of pyridyl) pyrazole was added 1.30 g (12.7 mmol) of acetic anhydride, and the mixture was heated at 110 ° C. for 4 hours. After the reaction mixture was concentrated under reduced pressure, ethanol was added to the residue and the mixture was concentrated under reduced pressure, and this operation was further repeated twice. The residue was suspended in 15 ml of ethanol, and 2.8 ml of a 1N aqueous sodium hydroxide solution (2.8 m
mol), and the mixture was stirred for 2 hours under ice cooling. A saline solution was added to the reaction solution, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with n-hexane to give 3-cyano-5 as crystals.
0.40 g of-(3-chloro-2-pyridyl) pyrazole was obtained. Yield 77%, melting point 204-205 ° C

Example 2 4-cyano-5- (5-ethyl-2-pyridyl) -3-
Trifluoromethylpyrazole (Compound No. II-1)
Manufacturing of

[0036]

Embedded image

(A) 5- (5-ethyl-2-pyridyl)
Preparation of 4-formyl-3-trifluoromethylpyrazole 4-bromo-1- (1-ethoxyethyl) -3- (5-
5.8 g (0.0148 mol) of ethyl-2-pyridyl) -5-trifluoromethylpyrazole in dried THF1
In a nitrogen stream at −78 ° C. under stirring.
1.69M n-butyllithium n-hexane solution 10.8
ml was added dropwise. After the reaction solution was further stirred at the same temperature for 1 hour, 1.8 g (0.0247 mol) of DMF was added. The temperature of the reaction solution was gradually raised to room temperature, and the mixture was stirred for 24 hours. Thereafter, an excess amount of an aqueous ammonium chloride solution was added. The reaction solution was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to obtain 4.75 g of a crude extract. 4.75 g of this crude extract was dissolved in 50 ml of methanol, and 10 ml of 1N hydrochloric acid was added dropwise with stirring. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, then, the reaction solution was concentrated under reduced pressure, and ethyl acetate and an aqueous solution of sodium hydrogen carbonate were added to the residue to separate the layers. After washing the ethyl acetate layer with saturated saline,
After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (benzene: ethyl acetate = 50: 1) to give 5- (5-ethyl-2-pyridyl). 0.4 g of -4-formyl-3-trifluoromethylpyrazole was obtained.
Yield 11%, melting point 141-143 ° C

(B) 5- (5-ethyl-2-pyridyl)
Production of 4-hydroxyiminomethyl-3-trifluoromethylpyrazole 5- (5-ethyl-2-pyridyl) -4-formyl-3
0.6 g of trifluoromethylpyrazole (2.23 mmol
l) was dissolved in 20 ml of ethanol, and 0.31 g (4.46 mmol) of hydroxylamine hydrochloride was added to sodium acetate.
0.37 g (4.51 mmol) was added, and the mixture was heated under reflux for about 2 hours. After evaporating the reaction solution under reduced pressure, ethyl acetate and water were added, the layers were separated, and the ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude extract (0.58 g).
I got Yield 63% ¹ H-NMR data of crude extract (CDCl ₃ , δpp
m): 1.47 (3H, t), 2.98 (2H, q), 8.17 (1H, dd), 8.9 (1H, d),
9.05 (1H, d), 9.25 (1H, s)

(C) 4-cyano-5- (5-ethyl-2)
Preparation of-(pyridyl) -3-trifluoromethylpyrazole 5- (5-ethyl-2-pyridyl) -4-hydroxyiminomethyl-3-trifluoromethylpyrazole 90 m
g (0.317 mmol) in 0.17 g of acetic anhydride (1.67 m
mol) and heated at 110 ° C. for 13 hours. After the reaction mixture was concentrated under reduced pressure, ethanol was added to the residue, and the mixture was further concentrated under reduced pressure. The residue was suspended in ethanol (10 ml), 1N-aqueous sodium hydroxide solution (5 ml) was added, and the mixture was stirred at room temperature for 2 hours. A saline solution was added to the reaction solution, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 4-cyano-5- (5-ethyl-2-pyridyl) -3-trifluoromethylpyrazole (50 mg).
I got Yield 63%, melting point 190-192 ° C

Example 3 Preparation of 4-bromo-3-cyano-5- (5-ethyl-2-pyridyl) pyrazole (Compound No. I-24)

[0041]

Embedded image

0.4 g (2 mmol) of 3-cyano-5- (5-ethyl-2-pyridyl) pyrazole was added to 10 ml of acetic acid.
And 4 ml of an acetic acid solution containing 0.4 g (2.5 mmol) of bromine was added dropwise at room temperature with stirring. After stirring at room temperature for 24 hours, the reaction solution was poured into ice water and extracted with ethyl acetate.
The ethyl acetate layer was washed with an aqueous solution of sodium hydrogen sulfite, an aqueous solution of sodium hydrogen carbonate and then water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with n-hexane and 4-bromo-3-cyano-
0.5 g of 5- (5-ethyl-2-pyridyl) pyrazole was obtained. 89% yield, 190-192 ° C melting point

Representative examples of the compounds of the present invention, including the compounds of the above Examples, are shown in Tables 1 and 2.

[0044]

[Table 101]

[0045]

[Table 102]

[0046]

[Table 103]

[0047]

[Table 104]

[0048]

[Table 105]

[0049]

[Table 201]

[0050]

[Table 202]

[0051]

[Table 203]

[0052]

[Table 204]

[0053]

[Table 205]

[0054]

[Table 206]

BEST MODE FOR CARRYING OUT THE INVENTION Since the compound of the present invention has excellent bactericidal activity against a wide variety of filamentous fungi, it is useful for controlling various diseases that occur during the cultivation of agricultural and horticultural crops including flowers, turf and pasture. Can be used. For example, rice blast disease (Pyricularia oryzae) Sheath Blight (Rhizoctonia solani) bakanae (Gibberella fujikuroi) Gomaha blight (Cochliobolus miyabeanus) barley brownish ear disease (Ustilago nuda) Wheat Fusarium head blight (Gibberella zeae) brown rust ( Puccinia recondita) Memonbyo (Pseudocercosporella herpotrichoides) glume blotch (Leptosphaeria nodorum) powdery mildew (Erysiphe graminis f. sp. tritici ) pink snow mold disease (Monographella nivalis) potato late blight (Phytophthora infestans) peanut brown spot disease (Mycosphaerella arachidis ) sugar beet brown spot disease (Cercospora beticola) cucumber powdery mildew (Sphaerotheca fuliginea) rot (Sclerotinia sclerotiorum) gray mold (Botrytis cinerea) downy mildew (Pseudoperonospora cubensis) tomato leaf blight (Cladosporium fulvum) late blight (Phytophthora infestans ) Eggplant Black blight ( Corynespora melongenae ) Onion Gray rot ( Botrytis all ii) strawberry powdery mildew (Sohaerotheca humuli) apple powdery mildew (Podosphaera leucotricha) scab (Venturia inaequalis) blossom disease (Monilinia mali) persimmon anthracnose (Gloeosporium kaki) Peach Haihoshibyo (Monilinia fructicola) grape powdery mildew (Uncinula necator) and downy mildew (Plasmopara viticola) without gymnosporangium (gymnosporangium asiaticum) black spot disease (Alternaria kikuchiana) tea Wamadarabyo (Pestalotia theae) and anthracnose (Colletotrichum theae-sinensis) citrus scab (Elisinoe fawcetti) It can be used to control blue mold ( Pennisillium italicum ), western grass, snow rot, and Sclerotinia borealis .

In recent years, various pathogens have developed resistance to benzimidazole agents, dicarboximide agents, and the like, resulting in a lack of efficacy of these agents, and there is a demand for an agent that is also effective against resistant pathogens. The compound of the present invention is not only sensitive but also has an excellent bactericidal effect against pathogenic bacteria resistant to benzimidazole agents and dicarboximide agents. Diseases that are more preferably applied include apple scab and cucumber gray mold. The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contacts such as ship bottoms and fish nets. Also, by mixing the compound of the present invention into paints, fibers, and the like, it can be used as an antibacterial and fungicide for walls and bathtubs, shoes and clothes. Some of the compounds of the present invention exhibit insecticidal, acaricidal and herbicidal activities.

[Bactericide] When the compound of the present invention thus obtained is actually applied, it can be used in a pure form without adding other components, and it can be used as a pesticide for general pesticides. It can also be used in the form to be obtained, that is, in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like. When the solid additive is intended as an additive and carrier, soybean grains, vegetable powder such as flour, diatomaceous earth,
Mineral fine powders such as apatite, gypsum, talc, bentonite, pyrophyllite, and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used. When a liquid dosage form is intended, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water Is used as a solvent. In order to obtain a uniform and stable form in these preparations, a surfactant may be added, if necessary. The wettable powder, emulsion, and flowable obtained in this manner are diluted to a predetermined concentration with water to prepare a suspension or an emulsion, and the powder and granules are used as they are by spraying them on plants.

Although the compound of the present invention exerts a sufficient effect even when used alone, it can be used in combination with one or more kinds of various fungicides, insecticides, acaricides or synergists.
Fungicides that can be used in combination with the compound of the present invention, insecticides,
Examples of the acaricide, nematicide, and plant growth regulator include the following.

Disinfectant: Copper agent: basic copper chloride, basic copper sulfate, etc. Sulfur agent: thiuram, maneb, mancozeb, polycarbamate, propineb, ziram, zineb, etc. Polyhaloalkylthio agent: captan, dichlorfluanide, phor Pets, etc. Organic chlorine agents: chlorothalonil, fthalide, etc. Organic phosphorus agents: IBP, EDDP, tolclofosmethyl,
Pyrazophos, fosetyl, etc. Benzimidazole agents: thiophanate methyl, benomyl, carbendazim, thiabendazole, etc. Dicarboximide agents: iprodione, vinclozolin, procymidone, fluoroimide, etc. Carboxamide agents: oxycarboxin, mepronil, flutranil, teclophthalam, triclamide, pencyclone, etc.

Phenylamide agents: metalaxyl, oxadixyl, furalaxyl, etc. SBI agents: triadimefon, triadimenol, bitertanol, microbutanyl, hexaconazole, propiconazole, trifumizole, prochloraz, pefurazoate, fenarimol, pyrifenox, triforine, flusilazole, Etaconazole, diclobutrazole, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazole, imazalil, tridemorph, fenpropimorph, butiobate, epoxyconazole, metconazole, etc.

Antibiotics: polyoxin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, etc. Others: propamocarb hydrochloride, quintozene, hydroxyisoxazole, metasulfocarb, anilazine,
Isoprothiolane, probenazole, quinomethionate, dithianone, dinocab, diclomedine, mepanipyrim, ferimzone, fluazinam, pyroquilon, tricyclazole, oxolinic acid, dithianone, iminoctadine acetate, simoxanil, pyrrolnitrin, metasulfocarb, dietofencaribine, citapfencarburinabine , Dozine, dimethomorph, phenazine oxide, etc.

Insecticides and miticides: Organophosphorus and carbamate insecticides: phenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb and the like. Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, protrin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, Cycloprothrin, trolametrin, silafluofen,
Blofenprox, Acrinasuri etc.

Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, cartap, thiocyclam, bensultap , Benzoepin, diafenthiuron, acetamiprid, nitenpyram, imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus. Nematicides: fenamiphos, phosthiazate and the like. Acaricides: chlorbenzilate, phenisobromolate, dicophor, amitraz, BPPS, benzomate,
Hexitiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulator: gibberellins (eg gibberellin A
_3, gibberellin A _4, gibberellin A ₇₎ IAA, NA
A.

[0063]

【Example】

[Bactericide] Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, and can be varied in a wide range. Parts in Formulation Examples are parts by weight.

Example 4 Water-dispersible powder 40 parts of the compound of the present invention 53 parts diatomaceous earth 53 parts higher alcohol sulfate 4 parts alkylnaphthalene sulfonate 3 parts If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 5 Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts 7 parts of polyoxyethylene alkyl allyl ether By mixing and dissolving the above, an emulsion having an active ingredient of 30% is obtained.

Example 6 Suspending agent 10 parts of the compound of the present invention 4 parts of sodium ligninsulfonate 4 parts of sodium dodecylbenzenesulfonate 1 part of xanthan gum 0.2 part of water 84.8 parts The above mixture was mixed until the particle size became 1 micron or less. If wet milled, a 10% active ingredient suspension is obtained.

[0067]

Next, Test Examples show that the compounds of the present invention are useful as effective components of various plant disease controlling agents. The control effect was determined by visually observing the growth of lesions and flora that appeared on leaves, stems and the like at the time of the survey, and calculating the control effect.

Test Example 1 Cucumber Gray Mold Control Test Cucumber cultivated in an unglazed pot (variety "Sagami Hanshiro")
The seedling was sprayed with the emulsion of Example 5 at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, inoculate a spore suspension (containing glucose and yeast extract) of cucumber gray mold fungus ( Botrytis cinerea ) into cucumber cotyledons, and in a dark, high humidity, constant temperature room (20 ° C.). 4
Held for days. The diameter of lesions on cotyledons was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed excellent effects of 75% or more. The compound numbers correspond to the compound numbers in Tables 1 and 2 (the same applies hereinafter). II, 2,3,4,5,6,7,8,9,10,1
2,15,17,19,20,22,23,24,2
5,26,27,28,29,30,32,33,3
4,36, II-1

Test Example 2 Apple Scab Control Test Apple seedlings (cultivar “Kunimitsu”, 3
~ 4 leaf stage), the emulsion of Example 5 was mixed with 200 ppm of the active ingredient.
At a concentration of After spraying, air-dry at room temperature, and scab of apple ( Venturia inaequalis )
Were maintained in a high humidity constant temperature room (20 ° C.) for 2 weeks, in which light and dark were repeated every 12 hours. As a result of comparing and investigating the appearance of lesions on the leaves with no treatment, the control effect was obtained,
The following compounds showed an excellent controlling effect of 75% or more. I-8, 10, 15, 19, 20, 22, 23, 24,
27, 28, 30, 31, 32, 33, 36, II-1

Test Example 3 Wheat Powdery Mildew Wheat seedlings (cultivar “Chihoku”) cultivated in unglazed pots
(0.1-1.2 leaf stage), the emulsion of the compound of the present invention was sprayed at a concentration of 200 ppm of the active ingredient. After spraying, air dry at room temperature, and wheat powdery mildew ( Erysiphe gra)
minia f. sp. Tritici) conidia were shaken off and inoculated and kept at room temperature of 22-25 ° C. for 7 days. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. I-15, 27, 36, II-1

Test Example 4 Test for controlling cucumber downy mildew Cucumber cultivated in an unglazed pot (variety "Sagami Hanshiro")
An emulsion of the compound of the present invention was sprayed on the seedlings at a concentration of 200 ppm of the active ingredient. After spraying, air dry naturally at room temperature to remove the cucumber downy mildew ( Pseudoperonospora cu)
a spore suspension of Bensis) was sprayed and inoculated and maintained 4 days in a thermostatic chamber of repeating light and dark and wet and dry every 12 hours (25 ° C.). The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed a control effect of 75% or more. I-7, 10, 20, 22, 23, 24, 25, 27,
28, 30, 33, 34, 36, II-1

Test Example 5 Test for Control of Grape Downy Mildew Leaves of an openly planted grape (variety “Kaiji”, 3rd grade) were punched into a 30 mm-diameter disc and immersed in a 200 ppm active ingredient chemical solution of the emulsion of Example 8. After immersion, air dry at room temperature, and the grape downy mildew fungus ( Plasmopara v
icola ) was spray inoculated with a zoosporang suspension and kept in a constant temperature room (20 ° C.) under illumination for 10 minutes . As a result of comparing and investigating the appearance of lesions on the leaves with no treatment, the control effect was obtained,
The following compounds showed an excellent controlling effect of 75% or more. I-15, 20, 23, 24, 25, 30, 32, 3
3,34, II-1

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinsuke Sano 345 Takada, Odawara-shi, Kanagawa Japan Nippon Soda Co., Ltd.Odawara Research Institute Co., Ltd. (72) Inventor Yuji Horikoshi 345 Takada, Odawara-shi, Kanagawa Nippon Soda Co., Ltd.

Claims (5)

[Claims] 1. A compound of the general formula (1) [Wherein X is a hydrogen atom, a halogen atom, a cyano group, C
_1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group or C _1-6
Represents an alkylsulfonyl group. R substitutes for a nitrogen atom of a pyrazole ring, and includes a hydrogen atom, a metal atom, C
_1-6 alkylcarbonyl group, C _1-6 alkylcarbonyloxy methyl group, C _1-6 alkylsulfonyl group, (halogen atom, may be substituted by C _1-6 alkyl or C _1-6 alkoxy group) A benzoyl group, a benzoyloxymethyl group (optionally substituted with a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group) or a (halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group) Represents a phenylsulfonyl group. Z is a halogen atom, a cyano group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkenyl group,
C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6
Haloalkynyl group, di C _1-6 alkylamino group, C _{1-6
Alkylthio} group, C _1-6 alkylsulfinyl group, C
_1-6 alkylsulfonyl group, C _3-8 cycloalkyl group,
Represents a C _3-8 cycloalkylmethyl group or a C _1-6 alkoxy group. m represents 1, 2, 3, and 4. Or a salt thereof. 2. A compound of the general formula (1-1) (Wherein, X, R, Z, and m represent the same meaning as described above), or the pyridylpyrazole compound or a salt thereof according to claim 1. 3. A compound of the general formula (1-2) (Wherein, X, R, Z, and m represent the same meaning as described above), or the pyridylpyrazole compound or a salt thereof according to claim 1. 4. A compound of the general formula (2) (Wherein X ¹ represents a hydrogen atom or a C _1-6 alkyl group, R ¹ represents a C _1-6 alkyl group, and Z and m have the same meanings as described above). Is reacted to give a compound of the general formula (3) (Wherein X ¹ , Z, and m have the same meanings as described above), and are subjected to a dehydration reaction, followed by a dehydration reaction. (Wherein X ¹ , Z and m have the same meanings as described above). 5. A compound of the general formula (1) (Wherein X, R, Z and m represent the same meaning as described above) or a pyridylpyrazole compound or a salt thereof.
A fungicide for agricultural and horticultural use, characterized by containing a seed or two or more kinds as an active ingredient.